Nitrobenzanthrone compound and process of making same.



. UNI ED STATES PATENT oFnreE.

OSCAR BALLY, or MANNHEIM, AND HUGO WOLFE, OF LUDWIGSHAFEN-ON-THE-RHINE,GER-

MANY, ASSIGNORS TO BADISOHE ANILIN & son. FABRIK, OFLUDWIGSHAFEN-ON-THE- BHINE, GERMANY, CORPORATION.

NrTRoBENzAnTImoNE-coMPoUND Ann PRooEssor MAKING SAME.

T all whom it may, concern:

Be-it known that'we, OSCAR BALLY and benzanthrone Compounds and Processes of Making the Same, of which the following is a specification.

We have discovered the t compounds which contain a benzanthrone group, not being coloring matters, such, for instance,'as benzanthrone itself and benzanthrone quinolin, and their derivatives, can, by means of a nitrating agent, such for instance as nitric acid, for whicha nitrateand sulfuric acid maybe used,

be easily converted into their nitro com-' pounds. The nitration is effected either in the presence of a solvent, or otherwise, and the roducts obtained. vary according to the -met 0d of working employed, the said products being either homogeneous compounds, or mixtures of .diiferent nitro compounds, which can be separated from one another, for instance by crystallization from glacial acetic acid, or nitrobenzenel The new nitrobenzanthrone compounds are well characterized bodies and are of use in the preparation of coloring matters. They consist generally of from brown to green crystals or crystalline owders and are soluble in concentrated sulihric acid yielding from yellowish red 7 to brown solutions and in twenty-three per cent. oleum yielding from red to brown solutions.

The following examples will serve to ill strate further the nature of our invention and.

how it can be carried into practical effect, but our invention is not confined to these examples. The parts are by weight, and the term peratures are given in degrees centigrade.

Example 1. Introduce one hundred (100) parts of finely divided benzanthrone into eight hundred and fifty (850) parts of'nitro benzene and add, at ordinary temperature, sixty-six (66) parts of eighty-seven (87) per centfnitric acid, whereupon the benzanthrone is dissolved, yielding a reddish-yellow solution. lV arm the mixture for from two (2),

. to three (3), hours, at a temperature of from forty (40), to fifty degrees and, then allow it to cool, whereupon a mass of crystals is obtained. Dilute with alcohol, filter, and

Specification of Letters Patent. 7 Application file d November 27. 1906. Serial No. 345.294.

wash with alcohol. The raw product so obtained consists of a crystalline powder which can be recrystallized from'glacla'l acetic acid, or from toluol, whereupon greenish yellow needles are obtained whlch melt af a temperature of two hundred and forty-four (244) degrees. Analysis points to their being "mono nitrobenzan'throne. The compound is soluble in most organic solvents yielding yellow solutions. It issoluble in concentrated sulfuric acid yielding a non-fluorescent golden yellow solution, and in twenty-three (23) per cent. oleum yielding a carmine solution 1 atentedJan.14,19O8.

which, upon warming, isconverted into a drill olive-green.

Example 2. Boil together, in a reflux apparatus, twenty (20) parts of benzahthrone and three hundred (300) arts of glacial acetic acid and add, graduafi a solution of twenty (20) parts -of eighty-seven (87) per cent. nitric acid in one hundred (100) arts of glacial acetic acid, so that the ad ition takes from two (2), to three (3), hours. Heat for about one (1) hour more untilnomore nitric acid fumes are evolved. The nitrobenzanthrone formed separates out partly during the reaction in greenish crystals and, upon cooling, a further quantity is obtained. Filter, wash with glacial acetic acid, and dry, Upon recrystallizing from glacial acetic acid and then from nitrobenzene small yellow needles are obtained which melt at a temperature of two hundred and ninety-eight (298) degrees. Analysis points to theirbeing mononitrobenzanthrone. They yield a reddish yellow solution in twenty-three (23) per cent.

oleum and this solution, upon warming,

-scarcely changes in.c olor. Example 3. Introduce ten (10) benzanthrone quinolin into one (1.00) parts ofeighty-se ven (87) percent. nitric acid, at a temperature, of from ten, to 15 (1045), degrees, at the same time cooling the whole, and then allow the mixture to stand, at ordinary temperature, for from two (2), tothree (3), days. The nitrobenzanthrone quinolin which is formed separates out of the solution in long yellow needles which can be filtered off by using an asbestos filter and then washed, first with sixty-two (62) per cent. nitric acid and then with water. The nitrobenzanthrone uinolin is a yellow powder difficultly solub em parts of most organic solvents, the solution being undredsulfuric acid yielding a non-fluorescent.

golden yellow solution, and in twenty-three (23) per cent. oleum yielding a reddish yellow solution which does not alter upon being heated. Upon the addition of water to the mother liquor of the nitration mixture a similar product, melting at a temperature of two hundred and eighty-two (282) degrees, can be obtained.

Example 4. Introduce ten parts of ben-' zanthrone quinolin sulfoacid into one hun dred (100) parts of eighty-seven (87) per cent. nitric acid, while cooling, and allow the solution to stand, at ordinary temperature, for about twenty-four (24) hours, and, when a test portion shows that no unaltered 'sulioacid is present, pour the solution onto ice. Filter, while cold, and wash with cold water. The nitrobenzanthrone quinohn sulfoacid obtained is a yellow powder diflicultlysoluble in cold. water, but more easily soluble in hot wate yielding a yellow solution. It is soluble in dilute caustic soda (the solution being yellowish brown) and in concentrated sulfuric acid and in twenty-three (23) per --cent. oleum yielding yellow-brown solutions with slight dark green fluorescence.

Example 5. Introduce fifty (50) parts of benzanthrone into three hundred (300) parts of eighty-seven (S7) per-cent. nitric acid, maintaining the temperature at front five to ten degrees. The benzanthrone is dissolvedyielding a reddish yellow solution. Then allow the solution to stand, at ordinary temperature, [or about fifteen hours, filter oil the nitro compound.

which separates out, in a King use oi an asbestos filter, and wash first with sixty-two (62) er cent. nitric .acid and then with water. The compound obtained consists chielly of dinitrobenzanthrone melting at a temperature of two hundred and sixty-eight (268) degrees. It is a green powder soluble in most organic solvents, thesolution being yellow. Its solution in concentrated sulfuric acid is yellow with a slight green fluorescence, and in twenty-three (23) percent. oleum the solution is yellowish rod, which does not change on warming.

Example 6. Introduce twenty parts of benzantl'irone sulioarid nc-pared from anthraquinone-2-sultoacid) into two hundred (200) parts oi? eighty-seven 87) per cent. nitric acid and allow the whole to stand, at ordinary temperature, for twentyfour (24) hours. Pour the solution into water, boil, and recipitate by means of common salt. Fi ter off the yellow flakes of nitrobenzanthrone sulfoacid, and Wash, and press them. The compound obtained is a yellow powder which is easily soluble in hot Water, the solution being. yellow. Its solution in caustic soda is ale red, in concentrated sulfuric acid ye low-red'with a yelloW-green fluorescence, and in twentythree (23) per cent. oleum reddish yellow without fluorescence. If desired, the henzanthrone sulfoacid can be nitrated in the presence of a solvent such, for instance, as

sulfuric acid. Analogous products can also be obtained if other benzanthrone sulfoacids be treated in a similar manner, such for instance as that obtainablefroin anthraqu1- none-l-sulfoacid, or. those obtainable by sul-- fonating benzanthrone.

Example-7. Dissolve twenty (20) parts of benzanthrone in four hundred (400) parts of ninety-seven (97) per cent. sulfuric acid and add, slowly, while stirring, at a temperature of from ten (10), to fifteen (15), degrees, the quantity of a nitrating acid (containing two hundred (200) grams ofpotassium nitrate per liter) theoretically necessary to convertthe benzanthrone into the mononitro compound, and then warm the whole for from three (3), to four (4), hours, at a temperature of'froni fifty to sixty degrees. Allow the melt to cool and our it onto ice, and filter oflf the product whic sepa-' rates out and wash, and dry it. The raw product so obtained is a greenish yellow owder which consists chiefly of a mixture oi two mononitrobenzanthrones which melt at tern peratures of two hundred and forty-four (244) and two hundred and ninety-eight (298) degrees respectively. It also contains small quantities of dinitrobenzanthronc which melts at a temperature of two hundred and thirty-six (2.36) degrees. It, in this example, double the quantity of 'nitrating acid be employed, a product is obtained which consists chiefly of the dinitrobenzanthrone described in example 5 and which. melts at a temperature of two hundred and sixty-eight (2 6S) degrees.

Example 8. Introduce ten (10) parts of benzanthrone quinolin into sixty (60) parts of nitrating acid (containing eighty-five per cent. nitric acid and fifteen (15) per cent. sulfuric acid.) at the same time cooling the whole. Then allow the solution to stand, at ordinary tempcrature ior about fifteen (15) hours and then heat for a 'lurther two (2), to three (3), hours at a temperature of from forty (40), to fifty (50), degrees. Allow the melt to cool, and pour it onto ice, and filter, wash, and dry, the nit-re product whic/l1 sepa rates out. It is a yellow powder which is insoluble in water and in alkalies, somewhat soluble in hot dilute acids, yielding a-ycllow solution, and, from this solution, it can, by means of alkali, be precipitated in the form ofyellowfiakes. It is dil'ficultly soluble in most organic solvents yielding yellow solu tions. 1n concentrated sulfuric acid it yields a yellow solution, and in twenty-three (23) er cent. oleum a nonfluorescent reddish yelow solution. .Upon rte-crystallization from nitrobenzene small glittering brown needles are obtained which melt at a temperature above three hundred and forty (340) degrees. Analysls'pomts to their being a dnutro come pound.

Now what we clann 1s:

1. The process of producing nitrobenzan throne'compounds by treating a hereinbcfore defined benzanthrone body with nitric acid;

2. The process of producmg mtrobenzanthrone compounds by treating a hereinbefore defined benzanthrone body with nitric acid in the presence of a solvent 3. As new'articles of manufacture the nitrobenzanthrone compounds which can be obtained by treating a hereinbefore defined benzanthrone body with nitric acid which new compounds can be obtained in the form be obtained in the form of greenish yellow needles melting at a temperature of about two hundred and forty-"four degrees centigrade and which is soluble in concentrated sulfuric acid yielding a non-fluorescent golden yellow solution and in twenty-three per cent. oleum yielding a carinine solution which upon warming is converted into a dull olive-green.

In testimony whereof we have hereunto set our hands in'the presence oi two subscribing witnesses.

.OSUAR' BALLY. HUGO wonrr.

Witnesses J Arno. LLOYD, H. WV. HARRIS. 

